Light-sensitive colloid silver halide photographic elements



United States Patent 3,158,484 LIGHT-SENSITIVE COLLOID SXLVTER HALIDE PHGTGGRAPHKC ELEMENTS Jozef Frans Willems, Wilriilr-Antwerp, Robrecht Julius Thiers, Brasschaat-Antwerp, and ,ioseph Louis De Munch, Beveren-Waas, Belgium, assignors to Gevacrt Photo-Producten N.V. Mortsel-Antwerp, Belgium, a Belgian company No Drawing. Filed Oct. 24, 1961, Ser. No. 149,809 Claims priority, application Great Britain, May 7, 1%59, 15,695/59; Netherlands, Get. 24, 1950, 257,213 2 (Ilaims. (Cl. 96-107) The present invention relates to a process for improving the quality of photographic materials, and more particularly to a process for enhancing the developability and general light-sensitivity of silver halide emulsion layers.

It is known that the general sensitivity of photographic emulsions which can be optimally sensitized throughout the whole range of the spectrum by means of the so-called chemical sensitizers, such as sulphur sensitizers, can be still further increased if polyglycols are added to these photographic elements (US. Patent Nos. 2,240,472 and 2,432,549).

It is also known that the same increase of sensitivity can be obtained by working up in the photographic material alkylene oxide polymers obtained by polymerizing alkylene oxide in the presence of hexitol ring dehydration products, aliphatic alcohols, aliphatic acids, amines, amides and phenols (US. Patent Nos. 2,400,532, 2,784,091 and 2,716,062).

It is further known that these polyglycols and alkylene oxide polymers should possess a molecular weight of at least 400 and in order to obtain a noticeable effect it is in practice necessary to use compounds which possess a molecular weight of 1500 to 2000 and more.

Contrary to the other known methods for increasing the sensitivity of silver halide emulsions such as those wherein the chemical sensitizers increase the inherent sensitivity and those wherein the cyanine dyes increase the spectral absorption, it appears that the final sensitivity of the silver halide emulsion layers wherein these compounds are incorporated is higher since these compounds exert a favorable influence on the development of these silver halide layers by means of the usual developers. These compounds can thus be considered as development accelerators.

It is, however, also known that these compounds, irrespective of the fact that they can be used as a compo nent in more sensitive silver halide layers, make these layers less suitable for storage and specially for storage at elevated temperatures and relative humidities, since these compounds considerably increase fog. It was further found that these compounds, when added to a photographic element for obtaining more sensitive silver halide emulsion layers, impair the image-tone of the developed silver obtained and give rise to brown and reddish-brown images.

It has now been found that the developability of the light-sensitive emulsions can be favorably influenced by adding to at least one emulsion layer or other layer comprised by the photographic element, compounds which are obtained by polycondensation of low-molecular alkylene oxide derivatives, showing no action on themselves, with functional linking agents.

On applying this new method, it was found that with these new compounds higher sensitivities can be obtained than with the known polyoxyalkylene compounds and also that these new compounds give rise to less fog on storage. Furthermore when using these new compounds, the imagetone of the developed silver remains unaltered.

These new compounds correspond to the following general formula:

R representsan alkylene group of from about 2 to about 3 carbon atoms including ethylene, propylene and isopropylene;

x and y each represent a positive integer equal to or higher than 2 and preferably less than about 35;

Q is a member of the group consisting of (1) A t'i}HOgroup, wherein R1 represents a hydrogen atom or an alkyl group containing from about 1 to about 4 carbon atoms; (2) A CRa%O-gtoup, wherein R3 represents a bivalent aliphatic hydrocarbon radical of from about 2 to 20 carbon atoms which radical may be interrupted by a hetero atom, or an arcmatic or heterocyclic radical including a group as described for R3;

(4) A P0group wherein R5 has the same significance as R2:

ll 7 (5) A POgroup wherein R5 has the same significance as R2;

0 R5 and (6) A -CHaCHOHRtCHOHOHeOgroup wherein Ra represents a chemical bound or a bivalent organic radical.

R is a member of the group consisting of (l) A hydrogen atom;

a a (2) A CHOH-group where Q represents a Ogroup;

(3) A (|fR E|1OHgroup where Q represents a (5) A -P group where Q represents a PO-group;

0 0 R2 H /v II (6) A P\ group where Q represents a lO-group;

represents a CHz-CH OH-Ra-CH OH-CHa-O-group.

phite, di-n-propyl phosphite, di-isopropyl phosphite, di-nbutyl phosphite and mixtures thereof, such as methyl ethyl phosphite. The trialkyl phosphites can also be employed With particularly good results being obtained from triethyl phosphite.

The epoxy compounds suitable for use in the instant invention include 1,2 di(2',3'-epoxypropoxy)ethane, 1,4 bis- (2,3'-epoxypropoxy)butane and similar epoxides including those more fully described in British patent specification No. 793,915. The polyepoxy compounds provide particularly good results.

The illustrative aliphatic aldehydes include formaldehyde, acetaldehyde, isobutyraldehyde, and isopropionaldehyde.

The carboxylic acids and anhydrides which can be used in the instant invention include maleic, succinic, phthalic, adipic, sebacic and diglycolic.

The ratio of the two reagents used in the condensation may vary Within wide limits and depends upon the desired properties which are intended to be ascribed to the condensation product. The ratios, however, must be judiciously selected so that water soluble condensation products are obtained. Suitable ratios are, for example, 1 mol of polyoxyalkylene compound and 1 mol of phosphonic acid ester or phosphoric acid ester; 1 mol of polyoxyalkylene compound and 0.5 mol of polyepoxide compound; 1 mol of polyoxyalkylene compound and 1 mol of aldehyde and 1 mol polyglycol per mol of acid or acid anhydride. However, it is to be noted that depending on the reagents selected, the ratios may vary over a relatively wide range so long as the condensate remains water soluble. Thus, operable ratios of polyoxyaikylene compounds to the second reagent vary from about 1:5 to :1. The selection of the proper ratio is Within the ability of one skilled in the art in view of the instant teaching.

The condensation products according to the instant invention can be prepared by mixing the reagents while heating at temperatures from slightly above ambient to above about 240 C. while stirring. The selection of the proper temperature depends upon the reagent chosen and upon the desired rate of reaction. As a rough rule of thumb, the rate for a given reaction is doubled for each rise in temperature. If desired, a suitable catalyst may be employed. It may be desirable at times to terminate the reaction by heating under reduced pressure.

More specifically, the compounds can be prepared:

(1) By polyacetalizing polyoxyalkylenes by means of an aliphatic aldehyde;

(2) By heating at about 200 C. polyoxyalkylenes with carboxylic anhydride such as maleic anhydride, succinic anhydride and phthalic anydride or with dibasic carboxylic acids such as for example adipic acid, maleic acid, sebacic acid and diglycolic acid;

(3) By heating polyoxyalkylenes with diisocyanates;

(4) By heating polyoxyalkylene compounds with dialkyl phosphites described more completely in the British patent specification No. 796,466; and

(5) By heating polyoxyalkylene compounds with a polyepoxide.

The following preparations will demonstrate illustrative condensation products employed in the instant invention.

PREPARATION 1 A solution of g. of polyglycol (average molecular weight: 400), 4.5 g. of paraformaldehyde and 3 drops of concentrated sulphuric acid in crn. of toluene is boiled for 2 days. The toluene is then distilled oif under reduced pressure. The residue is dissolved in chloroform and filtered. After evaporation of the chloroform, 16 g. of a viscous product are obtained.

PREPARATION 2 A solution of 25 g. of polyglycol (average molecular weight: 1000), 2.25 g. of paraformaldehyde and 3 drops of concentrated sulphuric acid in cm. of toluene is boiled for 2 days. Before filtering, another 50 cm. of toluene are added. The toluene is then distilled oil under reduced pressure. The residue is dissolved in chloroform and filtered. After evaporation of the chloroform the remaining powder is Washed with ether whereby 13 g. of a white powder are obtained.

PREPARATION 3 50 g. of polyglycol (average molecular weight: 1000), and 4.9 g. of maleic anhyd-ride are heated together under nitrogen atmosphere for 3 hours at 200 to 230 C. The reaction product obtained is washed with a mixture consisting of 4 parts of ether and one part of benzene. 30 g. of a light-brown solid substance soluble in water and alcohols are obtained.

PREPARATION 4 30 g. of polyglycol (average molecular weight: 300) and 4.9 g. of maleic anhydride are heated together under nitrogen atmosphere for 1 hour at 200 C. The reaction product obtained is washed with a mixture consisting of 3 parts of ether and 4 parts of benzene. After drying under vacuum, 17 g. of a viscous yellow oil are obtained.

PREPARATION 5 50 g. of polyglycol (average molecular weight: 1000) and 10 g. of sebacic acid are heated together under nitrogen atmosphere for 7 hours at 210 0., whereby water vapor evolves. On cooling, 52 g. of a resinous product which is quite soluble in water are obtained.

PREPARATION 6 50 g. of polyglycol (average molecular weight: 1000) are dissolved in anhydrous acetone to which 4.2 g. of hexamethylene diisocyauate are added. The reaction mixture is boiled for 7 hours whereafter the solvent is removed under reduced pressure. 52 g. of a white solid powder which is soluble in Water are obtained.

PREPARATION 7 30 g. of polyglycol (average molecular weight: 600), 6.7 g. of diglycolic acid and 3 g. of paratoluene sulphouic acid are heated under inlet of nitrogen for 1 hour at normal pressure and next for 5 hours at 2 mm. Hg. at 200 C. After cooling, a viscous oil which is quite soluble in water is obtained.

PREPARATION 8 20 g. of polyglycol (average molecular weight: 1000), 2.68 g. of diglycolic acid and 2 mg. of paratoluene sulphonic acid are heated for 1 /2 hours at normal pressure and for 5 hours at 2 mm. Hg at 200 C. After cooling, a viscous oil which is quite soluble in water is obtained.

PREPARATION 9 A solution of 30 g. of polyglycol (average molecular weight: 300) and 14.8 g. of phthalic anhydride are heated at 210 C. for 6 hours under nitrogen atmosphere. After cooling, a very viscous oil is obtained.

PREPARATION 10 A solution of 20 g. of polyglycol (average molecular Weight: 1000) and 3 g. of phthalic anhydride are heated at 210 C. for 6 hours under nitrogen atmosphere. After cooling, a resin is obtained.

PREPARATION 11 PREPARATION 12 50 g. (0.05 mol) of polyglycol (average molecular weight: 1000) dissolved in 125 cm. of tetrahydrofurane are dried over sodium sulphate and at 60-65 C. this solution is dropwise added within a period of 5 hours to a suspension of 10.9 g. (0.05 mol) of pyromellitic dianhydride in 75 cm. of tetrahydrofurane. The solution obtained is filtered over Norit and under vacuum evaporated on the water bath. The residue obtained is an oil which is washed with ether. Yield: 30 g. of end product.

PREPARATION 13 A mixture of 60 g. of polyethylene glycol (average molecular weight: 300) and 27.6 g. of diethyl phosphite, is gradually heated on the oil-bath under nitrogen atmosphere and in the presence of a trace of magnesium for 4 hours at 200 C., whereby 14 crn. of ethanol are distilled over. Then the reaction mixture is heated under reduced pressure for-4 hours at 200 C. The reaction product is obtained in the form of a very viscous oil which is quite water-soluble.

PREPARATION 14 A mixture of 100 g. of polyethylene glycol (average molecular weight: 1000) and 13.8 g. of diethyl phosphite is gradually heated on the oil-bath under nitrogen atmosphere in the presence of a trace of magnesium at 200 C. for 3 hours whereby ca. cm. of ethanol are distilled over. Then the reaction mixture is heated under reduced pressure for 4 hours at 200 C. The reaction product is obtained in the form of a quite water-soluble wax.

PREPARATION 15 A mixture of 100 g. of polyethylene glycol (average molecular weight: 1000) and 18.2 g. triethyl phosphate is gradually heated on the oil-bath under nitrogen atmosphere and in the presence of a trace of magnesium for3 hours at 200 C., whereby ca. 12 cm. of ethanol are distilled over. Then the reaction mixture is heated under reduced pressure for 4 hours at 200 C. The reaction product is obtained in the form of a quite water-soluble wax.

PREPARATION 16 To 30 g. of polyethylene glycol (average molecular weight: 300) heated under nitrogen atmosphere at 90 C., 1.25 g. of 50% aqueous potassium hydroxide is gradually added while stirring. After further heating of the reaction mixture for 45 minutes, 8.7 g. of l,2-di(2',3- epoxypropoxy)-ethane are quickly added. Then the mixture is heated for 90 minutes at 100 C. and finally neutralized with V; g. of 85% aqueous phosphoric acid. The reaction product is obtained in the form of a very viscous oil which is quite water-soluble.

PREPARATION '17 PREPARATION 18 To 200 g. of polyethylene glycol (average molecular weight: 1000) heated under nitrogen atmosphere at 90 C., 2.5 g. of 50% aqueous potassium hydroxide are slowly added while stirring. After further heating of the reaction mixture for minutes whereby the temperature rises to 100 C., 20.1 g. of 1,4-bis(2,3-epoxypropoxy)-butane are slowly added. Then the mixture is heated for 75 minutes at 100 C. and finally neutralized with 21 g. of 85% aqueous phosphoric acid. 208 g. of a reaction product are obtained in the form of a watersoluble wax. p

The compounds according to the invention may be added to the emulsions or brought into intimate contact with silver halide emulsion layers by dissolving them in water or in an aqueous mixture of organic solvents which do'not have a deleterious elfect on silver halide emulsions and .by adding the solution obtained to an emulsion or applying it to an emulsion layer as a coating composition. v The compounds can be introduced into the emulsion at various stages during its preparation; for example, they may be incorporated a a separate addition, or mixed with one or more of the other ingredients used at the initial precipitation of the silver halide grains, during the physical or chemical ripening process, or at some other point prior to coating the emulsion. Preferably, they are added after the chemical ripening and just before coating the emulsion.

The optimum amount of the compound to be added to the emulsion depends on the particular compound chosen, the nature of the colloid binding agent for the silver halide grains and the amount and kind of silver halide in the emulsion. In general, however, the compounds according tothe invention are added in a quantity of mg. to 7 gm.'per mol silver halide. If necessary, however, still other quantities of these compounds can be added which fall outside these limits.

The process of the present invention can be combined I with a method for increasing the sensitivity of the photo:

graphic material by incorporating therein small amounts of a sulphur-containing compound, such as allyl isothiocyanate, allyl thiourea and sodium thiosulphate, small amounts of reduction sensitizers such as the tin compounds described in Belgian specifications Nos. 493,- 464 and 568,687, the imino-aminomethane sulphinic acid compounds described in British specification No. 789,823 or small amounts of noble metal compounds such as of gold, platinum, palladium, iridium, ruthenium and rhodrum. As a matter of fact, the new process is advantageously superimposed on the sensitizing action of compounds originally present in gelatin.

By application of the method according to our present invention stabilizing agents such as, for example, mercury compounds and the compounds claimed and re ferred to in the statement of prior art of Belgian specifications Nos. 571,916 and 571,917 may be added to the emulsion. It is also usual to sensitize and/or to stabilize silver halide emulsions by incorporating therein cadmium salts or by carrying out their processing in the presence of cadmium salts. Still other ingredients such as antifogging agents, color couplers, developing substances,

hardening and wetting agents, can moreover and without deleteriously affecting the emulsion, be added thereto in a manner known to those skilled in the art.

As a result of their developability, the new compounds are elfective in increasing the X-ray sensitivity and the general light sensitivity of orthochromatic, panchromatic, and all special emulsions, as well as of the ordinary non-spectrally sensitized ones. Thus, they can be added without or with optical sensitizing dyes and in the latter case before or after them. They are also useful with a variety of emulsions, since the production of pronounced speed is increased in either negative or positive types of emul- SlOl'lS.

Having described the invention in general terms, the

property of conferring a better 7 Example 1 A Washed coarsely grained gelatino silver iodo-b romide negative type of emulsion (average grain size 0.8 wherein the silver halide consists of 94.5 mol percent Example 4 The following results were obtained in exactly the same manner as described in Example 1.

silver bromide and 5.5 mol percent silver iodide is rip- Rel? ened at 45 C. After addition of a panchromatic senample Compound added g Gamma o sitizing dye and other usual ingredients the emulsion is coated onto a suitable support (sample 1). Further samples were prepared by adding prior to coating to the n 100 [161 0 13 same emulsion and per mol s1lver halide present the 3-2 ggg gggg t gg g -f i3 8% i amollllnts of developing accfleritgrs :listed belgw. They 5 corgpmg f g g gjgg 1% are t en treated as samp e ter rying an exposure s 001111101111 0 p p 0. they are developed for 7 minutes at 20 C. in a solution gif fgfiggfi i fifiigfiggg fig IZ 8% g. compoun o prepar. 0. consisting of 0.34 g. compound of proper. 10- 112 0.72 0.16 Water crn. 800 3.4g.eomponndofprepar.10 125 0.78 0.10 Monomethyl-p-aminophenol sulphate g 2 Hydroquinone g 5 Example 5 Sulphlte (anhydrous) g? A washed coarsely grained gelatino silver iodo-brornide i &- 5 emulsion wherein the silver halide consists of 98.2 mol -"1g 0 5 percent silver bromide and 1.8 mol percent silver iodide otassmm 5862 6 "g" is ripened at 42 C. After addition of a stabilizing agent Water up to such as S-hydroxy-7-methyl-s-triazo1o-(4,5a)-pyrimidine SENSITOMETRIC RESULTS and of other usual ingredients, the emulsion is coated onto a suitable support (sample 1). e Further samples were prepared by adding to the same sample Compound added 252 Gamma Fog emulsion prior to coating and, per mol silver halide presy ent, the amounts of developing accelerators listed below.

They are then treated as sample 1. After drying and ex- 1 NImp 100 75 06 posure they are developed for 4 minutes in a solution con- 2 0.12100. polyglycol average n1.w.. 98 0.71 0.06 Sisting of: 3 0.34 l 1 001 a era- 0 m.w.: 103 0.59 0.08

1,0i0. yg y V g 1 Water 0111. 800 4 0.34 g. compound of prepar. 1 13 0.76 0.06 Mono methyl p amino Phenol Sulphate g 4 0.31 1 i re a .2 129 0.77 0.06 5 g p0 ymero p p r Sodium sulphlte (anhydrous) g 65 Exam {8 2 HYd r0quin0ne g 0 p Sodium carbonate (anhydrous) g The following results were obtained in exactly the Potassium bromide g 5 same manner as described in Example 1. Water up to 1000 cm SENSITOMETRIC RESULTS 4fterb36thr. of

mcu n 1011 Sample Compound added SRel. Gamma Fog Rel. Gamma Fog Sens.

100 s. 27 0. 04 100 0.09 131 3.28 0.05 120 3 00 011 0.2g. prep.8 131 3.02 0.00 135 0.16

Example 6 Rela- Sample Compound added tive Gamma Fog Two samples of an emulsion such as that of Example 1 @2 2; are considered. To sample 1 are added per mol of silver halide and before coating, 0.40 g. polyglycol with an w m 100 M8 (m6 average molecular weight of 6000. To sample 2 of the $111111: 32 pi iii'Z1=i;'iiw.' as 0.56 0.06 same emulsion is added before coating, instead of 0.40 g.

- 2 l 1 col with an average molecular weight of 6000 1 1 a e m.w.: 111 0. 00 0.08 01 P Y Y 3 Yea aver g 0.40 g. of the compound of Preparation 2. 4 3i ggfi iifiii 3i 3; 2; 813g These two samples were packed and stored for one year 5 p in a relatively moist atmosphere at temperatures fluctu- V E xample 3 The following results were obtained in exactly the same manner as described in Example 1.

ating between 15 and 35 C. After this year, they were exposed to light and developed for 7 minutes in a developer such as that of Example 1.

lzela- G F Sample Compound added sRel. Gamma Fog ound added ive amma 0g ens. Sample Comp tivi y 1 0.125 g.0 poly glycol average m.w.: 100 0.80 0.18

,00 N009 100 65 0110 2 0.4 g. compound of prepar. 2 100 0, 7g Q12 0.34 g. polyglycol average m.w.: 98 0.65 0.10

3 O. 3.4 g. polyglyc-ol average m.w.: 93 0.65 010 Example 7 111 0. 07 0.13 i g'c iri i iiiid oibi g ii3i. 119 0. 0a 0.14 Two samples of an emulsion such as that of Example 0.34g- P I;gglg; 8'2: mg n 5 are considered. To sample 1 is added 0.2 g. of Carbog' eompmm p p M wax 6000 which is the optimal allowable amount for not producing an CXCCSS Of fog. T0 sample 2 Of the same SENSITOMETRIG RESULTS) emulsion are added such amounts of compounds according to the present invention until the same highest allow- 7 I able fog is attained, and next the sensitivities obtained Sample Compound added gg a a Fo are checked after 4 minutes of development such as in 5 my Example 5.

None 100 0. 60 0. 0.34 g. polyethylene glycol (aver- 98 0. 65 0. 10 Z i 19 i 1 1 9s 0 e5 0 10 t e 1 Sample Compound added Rel. Gamma 3 g yea (av r Sens 0.3% g. compound of preparation 105 0.64 0.11

1 5.3 g. compound of preparation 13 109 0. 64 0. 12 1 Carbowax 6000 100 0.34 g. compound of preparation 111 0.64 0.11

1 g. compound of prepar. 3 123 8. 50 0.06 14. 2 Carbowax 6000 100 5O 07 3.4 g. compound of preparation 14. 128 0.74 0. 12 u 1 compound of Prepar- 114 25 05 8 3.4 g. compound of preparation 15. 132 0. 85 0. 13

Example 10' Exam le 8 The following results were obtained in exactly the same To one sample of an emulsionaccording to Example 5 manner as described i Example 9 is added before coating 0.2 g. of Carbowax (sample 1) and to another sample 0.2 g. of compound according to Rem preparation 8 (sample 2). Both samples are stored for Sample Compound added tive Gamma Fog some days at considerable relative humidity and high temperature, and next developed for 4 minutes in developer from Example 1 None 100 0,4 0.08 2 0.333 g. compound of preparation 102 0.48 0.09 a 3.4. compound of preparation 16. 106 o. 54 0. 09 4 3.4 g. compound of preparation 17. 105 0. 50 0. 09

Sample Compound added S12E15. Gamma Fog 5 3.4 g. compound of preparation 17. 115 0. 58 0. 12

1 0,2 g, Carbowax e000 100 2.93 0.17 Example 11 2 compmmd 8 116 The following sensi-tometric results are obtained in the same manner as described in Example 9, but the samples are developed for 7 minutes at 20 C. in a solution of the Example 9 following composition:

A washed coarsely grained gelatin silver iodobromide W t 300 negative type of emulsion (average grain size 0.8 ,u) M th l. i h l ulfat 6 wherein the silver halide consists of 94.5 mol percent Hydroquinone g 3 silver bromide and 5.5 mol percent Silv r i d e is ripen Sodium sulphite (anhydrous) g 75 at C. After addition of a panchromatic sensitiz ng 40 Sodium c rb te (anhydrous) g 5 dye and other usual ingredients the emulsion is coated Borax 10 onto a suitable support (sample 1). Further samples W t up to 1000 e After 36 h. of incubation Relative Sample Compound added I Sensi- Gamma Fog Relativity tive Gamma Fog sensitivity 1 None 100 0.98 0.13 100 0. 80 0.16 2 0.34 g. Carbowax 6000 (trade name of Union 106 1.07 0.19 106 0.91 0.28

Carbide and Carbon, New York, N.Y., U.S.A., 1"or a polyalkylene glycol with aver. mol. weight of 6,000). 3 3.4 g. compound of preparation 14 111 1.15 0.16 112 0.88 0.26

were prepared by adding prior to coating to the same Example 12 emulsion and per mol silver halide present the amounts of developing accelerators listed below. They are then A Washed coarsely grallled gelatine Silver ifldObrOmide treated as sample 1. After drying and exposure they are emulsionwherein the silver halide consists of 98.2 mol developed for 7 minutes at 20 C. in a Solution 0011- percent silver bromide and 1.8 mol percent silver iodide is sistrng of: ripened at 42 C. After addition of a stabilizing agent Water 300 such as 5 -hydroXy-7-methyl-s-triazolo-(2.3a) -pyrimidine M y -p- P1181101 phate g and of other usual ingredients, the emulsion is coated Hydroquinone 3 onto a suitable support (sample 1).

1 3211 sulphlte (anhydrous) "g" Further samples were prepared by adding to the sanie Boric a emulsion prior to coating and, per mol silver halide pres- Potassium bromide 5 cut, the amounts of developing accelerators listed below.

Water up to 1000 cm. y are {refitted as pl After drying and exposure they are developed for 4 minutes in a solution consisting of:

Water cm. 800 Mono-methyl-p-amino phenol sulphate g 4 Sodium sulphite (anhydrous) g 65 Hydroquinone g 10 Sodium carbonate (anhydrous) g 45 Potassium bromide g 5 Water up to 1000 cm.

SENSIT OMETR IC RESULTS L wherein:

R is an alkylene group of from 2 to 3 carbon atoms;

After 36 h. of incubation Relative Sample Compound added Sensi- Gamma Fog Relativity tive Gamma Fog sensitivity None 100 3.10 04 111 3 24 0.09 2 g. compound of preparation 14 121 3. 46 0 05 120 3 32 0. 12 4 g. compound of preparation 16.- 121 3. 2O 0 04 127 2 97 0. 09 0.8 g. compound of preparation 17 116 3. 12 0 04 1% 2 89 0. 08 1.6 g. compound of preparation 17 128 3. 22 0 05 130 2 81 0.

Although in the above examples gelatine silver halide emulsions are described, our invention is not limited to such colloid emulsions. Emulsions based on other waterpermeable colloids may equally well be treated according to the present invention. Among such colloids are for instance to be mentioned: agar-agar, zein, collodion, water-soluble cellulose derivatives such as hydrolyzed cellulose acetate; cellulose esters of hydroxycarboxylic acids, for example lactic or glycolic acid; alkali metal salts of cellulose esters of dicarboxylic acids such as phthalic acid; polyvinyl alcohol, and partially hydrolyzed polyvinyl acetate and interpolymers of vinyl acetate with unsaturated compounds such as styrene and maleic acid, water-soluble polyvinyl acetals and other hydrophilic synthetic or natural resins or polymeric compounds.

The new developing accelerators may be used for sensitizing the known types of silver chloride, silver bromide, silver iodide emulsions and emulsions containing mixtures of these halides.

Furthermore, the methods as described in the above examples are not limited, as far as the quantity and the nature of the developing accelerator to be added or the moment of the addition are concerned. Indeed, for obtaining an optimum efiect, all particular techniques in the preparation of light-sensitive emulsions should be taken into account.

An advantage of this invention is the compatability of the new developing accelerators with color couplers and optical sensitizing dyes, which fact is of great importance for using the new developing accelerators for increasing the general light-sensitivity of color photographic material containing one or more light sensitive layers.

A further advantage of the process lies in the simplicity of its general application as for instance in the manufacture of light-sensitive materials for amateur and professional photography and cinematography, for motion pictures, for graphic processes and for scientific and industrial applications.

It should be appreciated that the invention is not to be construed to be limited by the illustrative examples. It is possible to produce still other embodiments without departing from the inventive concept herein disclosed.

This application is a continuation-in-part application of the Willems et a1. co-pending application, Serial No. 27,484, filed May 9, 1960.

What is claimed is:

1. A light-sensitive photographic material comprising a support and at least one gelatino silver halide emulsion layer containing an alkylene oxide polymer in an amount between 0.2 g. and 7.00 g. per mol silver halide, said alkylene oxide polymer being a condensation product of (1) a FHO group, wherein R2 is a member of the group consisting of hydrogen and an alkyl radical containing [tom 1 to 4 carbon atoms.

bivalent aliphatic hydrocarbon radical of from 2 to 20 carbon atoms;

(3) a -PO- group wherein R5 has the same value as R2;

II (4) a. PO group wherein R5 has the same value as R2; and

(5) a CHTCH OHR -OHOHOHZO group wherein R is a member of the group consisting of a chemical bond and a bivalent polyether radical;

R is a member of the group consisting of (1) a hydrogen atom; (2) a -CHOH group where Q represents a -(|3HO- group;

' CR3 (4) a i group where Q is a -PO- group;

0 OR: (5) a i group where Q is a %0 group;

(5R2 (5R3 (6) a --CHz-GHOHRC 13-}3H2 group where Q is a 2. A light-sensitive photographic material comprising a support and at least one gelatino silver halide emulsion 7 layer containing an alkylene oxide polymer in an amount sisting of an aliphatic aldehyde, and an aliphatic diisocya- 13 14 nate, said alkylene oxide polymer having the general H formula: I

(3) a ON-(OH2)n N=C=O group wherein n is a. positive RO(CH CH O) Q,(CH CH O)x R H wherein x represents a positive integer from 2 to 35, y represents a positive integer from 2 to 20, Q represents a member selected from the groupeonsisting of 5 integer from 2 to 20.

References Cited in the file of this patent UNITED STATES PATENTS H H 10 1,970,578 Schoeller et al Aug. 21, 1934 g%) n group, wherein is a Positive 2,630,424 Gresham Mar, 3, 1953 2,716,062 Carroll et al Aug. 23, 1955 and R is a member selected from the group consisting of Schwartz et 9 i f i i g g Detergents (1) ahydmgen atom vol. 11, pages 131-2, Interscience Publishers, Inc., New (2) a OHBOH group,

York (1958). 

1. A LIGHT-SENSITIVE PHOTOGRAPHIC MATERIAL COMPRISING A SUPPORT AND AT LEAST ONE GELATINO SILVER HALIDE EMULSION LAYER CONTAINING AN ALKYLENE OXIDE POLYMER IN AN AMOUNT BETWEEN 0.2 G. AND 7.00 G. PER MOLE SILVER HALIDE, SAID ALKYLENE OXIDE POLYMER BEING A CONDENSATION PRODUCT OF A POLYALKYLENE GLYCOL WITH A MOLECULAR WEIGHT BETWEEN 100 AND 1500, AND AN ORGANIC COMPOUND OF THE CLASS CONSISTING OF AN ALIPHATIC ALDEHYDE, AN ALIPHATIC DIISOCYANATE, ALKYL PHOSPHITES, ALKYL PHOSPHATES AND POLYEPOXIDES, SAID ALKYLENE OXIDE POLYMER HAVING THE GENERAL FORMULA: 